Low voltage E-paper

ABSTRACT

A cholesteric display including a liquid crystalline mixture having a dipolar dopant dissolved in the liquid crystalline mixture and the resulting mixture is reflecting light in the visible range of the spectrum when in planar state. In accordance with another aspect, a process includes forming a composition with a dipolar molecule to result in a liquid crystal dipolar dopant, and liquid crystal is added to the composition. In accordance with still another aspect, a device includes a liquid crystal composition includes a cholesteric liquid and a dipolar dopant. The liquid crystal composition is switchable between a focal-conic state and a planar state in the presence of an electric field and is stable in the respective state when the electric field is removed.

BACKGROUND

Illustrated herein in embodiments are liquid crystal displays and, morespecifically, bistable cholesteric liquid crystal displays (LCDs).

Cholesteric liquid crystal displays have attracted attention in recentyears as an electronic paper (e-paper) type of display device. Thecholesteric liquid crystal display is capable of utilizing reflectionfrom surrounding lights as a light source and has a storage propertywhich can hold display contents after the supply voltage is turned off.Further, because an active matrix is not needed for driving the display,cholesteric liquid crystal display devices are capable of providinglarge-capacity displays, and may use a flexible substrate which isparticularly suitable for e-paper.

The cholesteric liquid crystal is made up of spirally oriented rod-likemolecules (mesogens), and exhibits a selective reflection phenomenonthat reflects a light of a wavelength corresponding to a spiral pitch.The cholesteric liquid crystal display elements utilize this phenomenon.The cholesteric molecules can, under appropriate conditions, be in oneof several different general orientations, namely, a planar orientation,a finger-print orientation, a focal-conic orientation, and a homeotropicorientation, as shown in FIGS. 1A-1B respectively.

The planar orientation shown in FIG. 1A is a state in which thecholesteric molecules 10 are aligned between two substrates 12, 14 in ahelical spiral axis oriented vertical to the substrate plane.Cholesteric liquid crystals in the planar texture possess the opticalproperty of separating incident white light into its left and right-handcircular components by reflecting one component and transmitting theother. This is due to the regular helical alignment of the cholestericmolecules in a spatially periodic twisted helical structure. Forsuitably chosen pitches, the reflected component is in the visiblerange, i.e., from about 400 nm to about 730 nm, giving rise to aselective color being observed.

The finger-print orientation shown in FIG. 1B is a state in which thespiral axis is oriented essentially parallel to the substrate plane. Inpractice, because of the anchoring effect of the surfaces of the cell,there are defects in this orientation and the helical axes of thedomains may be more or less randomly oriented through the cell. Thisstate is referred to as focal-conic and is schematically shown in FIG.1C. The focal-conic state is made up of multiple domains, each havingthe same helical pitch, with the helical axes arranged approximatelyparallel to the substrates. In the focal-conic state, the cell is weaklyscattering (nearly transparent) and transmits most of the incidentlight. When the bottom of the display is coated with a light absorptivelayer 16, the color of the absorptive layer 16 is observed, which isusually black.

The homeotropic orientation shown in FIG. 1D is a state in which thespiral structure is decomposed and the cholesteric molecules 10 areoriented perpendicular to the substrate plane, also in a colorlessstate, and the color of the light absorptive layer 16 is observed.

To date cholesteric display technology has frequently employed switchingbetween the planar state and the focal-conic state by means of electricfields being applied between electrodes 18, 20 affixed or adjacent tothe substrates 12, 14. To obtain the reflective colored state, arelatively high voltage is necessary, up to 100-200 V for example,depending on the liquid crystal and the thickness of the display. Forthis reason, it is difficult to use such a display for fabrication ofelectronic paper, which ideally should use a low voltage for switching,preferably low enough that the display could be operated utilizing abattery power source for example.

Therefore, there is a need for a means of switching a cholestericdisplay with a lower voltage than presently required, thereby providinga more practical embodiment of electronic paper which consumes lesspower than present designs.

BRIEF DESCRIPTION

In accordance with one embodiment of the disclosure, there is provided abistable cholesteric display including a cholesteric liquid crystallinemixture having a dipolar dopant dissolved in the cholesteric liquidcrystalline mixture.

In accordance with another embodiment of the disclosure, there isprovided a process including forming a composition with a dipolarmolecule to result in a liquid crystal dipolar dopant, and adding aliquid crystal to the composition.

In accordance with still another embodiment of the disclosure, there isprovided a device having a liquid crystal composition including acholesteric liquid and a dipolar dopant. The liquid crystal compositionis switchable between a focal-conic state and a planar state in thepresence of an electric field and is stable in the respective state whenthe electric field is removed.

These and other non-limiting aspects of the development are moreparticularly disclosed below.

BRIEF DESCRIPTION OF THE DRAWINGS

The following is a brief description of the drawings, which arepresented for the purposes of illustrating the development disclosedherein and not for the purposes of limiting the same.

FIG. 1A is a simplified elevational view of a conventional cholestericliquid crystal display device in a planar state;

FIG. 1B is a simplified elevational view of a conventional cholestericliquid crystal display device in a finger-print state;

FIG. 1C is a simplified elevational view of a conventional cholestericliquid crystal display device in focal-conic state.

FIG. 1D is a simplified elevational view of a conventional liquidcrystal display device in a homeotropic state;

FIGS. 2A-2C are simplified elevational views of an embodiment of aliquid crystal display in a various states, and having a dipolar dopant;

FIG. 3 depicts a process for producing a dipolar dopant according toembodiments of the present disclosure;

DETAILED DESCRIPTION

This disclosure relates to a cholesteric display including a liquidcrystalline mixture having a dipolar dopant dissolved in the liquidcrystalline mixture and the resulting mixture is reflecting light in thevisible range of the spectrum when in planar state. In accordance withanother aspect, a process includes forming a composition with a dipolarmolecule to result in a liquid crystal dipolar dopant, and liquidcrystal is added to the composition. In accordance with still anotheraspect, a device includes a liquid crystal composition includes acholesteric liquid and a dipolar dopant. The liquid crystal compositionis switchable between a focal-conic state and a planar state in thepresence of an electric field and is stable in the respective state whenthe electric field is removed.

A more complete understanding of the processes and apparatuses disclosedherein can be obtained by reference to the accompanying drawings. Thesefigures are merely schematic representations based on convenience andthe ease of demonstrating the present development, and are, therefore,not intended to indicate relative size and dimensions of the displaydevices or components thereof and/or to define or limit the scope of theexemplary embodiments.

Although specific terms are used in the following description for thesake of clarity, these terms are intended to refer only to theparticular structure of the embodiments selected for illustration in thedrawings, and are not intended to define or limit the scope of thedisclosure. In the drawings and the following description below, it isto be understood that like numeric designations refer to components oflike function.

With reference to FIG. 2, embodiments of the present disclosure usedipolar molecules 22 as dopants in the cholesteric mixture 24 of acholesteric display. The dipolar molecules 22 are electrically neutralmolecules which carry a positive and a negative charge in one of theirmajor canonical descriptions. Because of this, the dipolar moleculespossess a unidirectional dipole moment which aligns essentially parallelto an externally applied electric field 26 such as shown in the firstblack state 28 as shown in FIG. 2A. When the direction of the appliedelectric field 26 is reversed, the dipolar molecules 22 will tend toreorient in the opposite direction, or in other words, rotate 180degrees. If the reversed field is applied for a sufficiently long time,a second black state 30 is achieved as shown in FIG. 2C. However, if theelectric field 26 is reversed, but applied for only a very short time (ashort pulse), an intermediate planar, colored state 32 can be obtained.See FIG. 2B. Each of the two states, planar, i.e. colored and focalconic, i.e. transparent, is stable when the electric field is removed.

Suitable cholesteric liquid crystal mixtures include for example BLmixtures available from EM Industries, Inc. (BL088, BL 90, BL94 andBL108 as a few examples). The helical pitch is tuned to the desiredrange by mixing this cholesteric liquid crystal mixture with a nematicliquid crystal. Examples of nematic liquid crystal BL mixtures availableat EM Industries, Inc., include BL001 (E7), BL002 (E8), BL033 (versionof BL002) and BL087, and 5CB (commercially available at Sigma-Aldrich).The cholesteric liquid crystal composition is adjusted in such a way asto reflect light in the visible range (i.e., about 400 nm to about 730nm) when is aligned in its planar state.

When the dipolar molecules 22 are present in the cholesteric mixture 24,the rotation of the dipolar molecules induced by application of theexternal electric field also induces rotation of the cholesterichelices, changing the appearance of the display. When, during theinduced rotation, the helices are perpendicular to the displaysubstrate, the colored planar state 32 is observed. When the helices areparallel to the substrate, or at least in a disordered random state, thecholesteric mixture appears transparent. If the display substrateopposite the observer is coated with a black absorptive layer, theobserved color is black as represented by the first and second blackstates 28, 30. See FIGS. 2A and 2C.

Because the dipolar molecules possess the above-described positive andnegative charges, they are more sensitive, or responsive, to anexternally applied electric field when compared with the non-polarcholesteric liquid mixture. Therefore, cholesteric displays havingdipolar molecules as dopants advantageously may be operated at a lowervoltage when compared with conventional cholesteric displays.

The dipolar dopant 30 comprises an electron donor group and an electronacceptor group connected at the ends of a conjugated path. This resultsin the general structure: Donor—Conjugated Path—Acceptor. To ensuremiscibility of the dipolar dopant and the liquid crystal, a liquidcrystal compatibilizing moiety is attached to the dipolar dopantmolecule. The electron donor is an atom or a group of atoms that have anegative Hammett parameter. The electron acceptor is a group of atomshaving a positive Hammett parameter. Donor group is selected from anatom selected from the group consisting of N, O, S, and P, where thevalence of the atom is satisfied by bonding to at least one other moietyto satisfy the valence of the atom; the other moiety or moieties tosatisfy the valence of the atom selected as the electron donor moietymay be for instance a hydrogen atom, or short hydrocarbon group such asa straight alkyl chain having for example 1 to about 3 carbon atoms.

The conjugated bridging moiety may be any suitable group through whichelectrons can pass from the electron donor moiety (D) to the electronacceptor moiety (A). In embodiments, the conjugated bridging moiety (C)is a π-electron conjugated bridge that is composed of for example (thereis no overlap among the categories (a), (b), and (c) described below):

(a) at least one aromatic ring such as one, two or more aromatic ringshaving for instance from about 6 carbon atoms to about 40 carbon atomssuch as —C6H4-, and —C6H4-C6H4-;

(b) at least one aromatic ring such as one, two or more aromatic ringsconjugated through one or more ethenyl or ethynyl bonds having forinstance from about 8 carbon atoms to about 50 carbon atoms such as—C6H4-CH═CH—C6H4-, and —C6H4-C≡C—C6H4-; and

(c) fused aromatic rings having for instance from about 10 to about 50carbon atoms such as 1,4-C10H6 and 1,5-C10H6.

The electron acceptor moiety (A) may be any suitable atom or groupcapable of accepting electrons. In embodiments, the electron acceptormoiety (A) is an electron withdrawing functional moiety which-accordingto Hammett equation possesses a positive Hammett constant. The electronacceptor moiety may be for example the following:

(a) an aldehyde (—CO—H);

(b) a ketone (—CO—R) where R may be for example a straight chain alkylgroup having for example 1 to about 3 carbon atoms, such as methyl,ethyl, propyl and isopropyl.

(c) an ester (—COOR) where R may be for example a straight chain alkylgroup having for example 1 to about 3 carbon atoms, such as methyl,ethyl, propyl and isopropyl.

(d) a carboxylic acid (—COOH);

(e) cyano (CN);

(f) nitro (NO2);

(g) nitroso (N═O);

(h) a sulfur-based group (e.g., —SO2-CH3; and —SO2-CF3);

(i) a fluorine atom;

(k) a boron atom.

The liquid crystal compatibilizing moiety can be connected to the donorgroup, acceptor group or conjugated path group. The liquid crystalcompatibilizing moiety (S) may be any suitable group that increasesmiscibility of the liquid crystal domain stabilizing compound with theliquid crystal. The liquid crystal compatibilizing moiety (S) may be forexample the following:

(a) a substituted or unsubstituted hydrocarbon having for example 1 toabout 30 carbon atoms.

(b) a heterocyclic moiety having for example from 5 to about 15 atoms(referring to number of carbon atoms and heteroatom(s), where theheteroatom can be for instance N, O, S, P, and Se. Exemplary examplesinclude: piperidine, ethyl-piperidine, methylpirrolidine.

(c) a hetero-acyclic moiety having for example from 5 to about 15 atoms(referring to number of carbon atoms and heteroatom(s), where theheteroatom can be for instance N, O, S, P, and Se. Exemplary examplesinclude: glycol and polyglycol ethers, alcohol moieties like for example2-hydroxy-ethyl, and thiol moieties like for exampleethyl-2-methyl-ethyl-thioether.

In embodiments, the liquid crystal compatibilizing moiety (S) may be ahydrocarbon optionally substituted with for example a liquid crystalmoiety, a heterocyclic moiety optionally substituted with for example aliquid crystal moiety, or a hetero-acylic moiety optionally substitutedwith for example a liquid crystal moiety.

The dipolar dopant can be a small molecule or a macromolecule. Amacromolecule type of dipolar dopant requires that the precursor monomerto have at least one polymerizable group (Z). The polymerizable moietiesmay be any monomers that can be polymerized to form an oligomer/polymer.Suitable monomers include those having a double bond (—CH═CH2) or triplebond capable of being polymerized such as acryl or ethenyl.

In one embodiment, with reference to FIG. 3, to ensure a goodmiscibility between the dipolar dopant and the cholesteric liquidcrystal, a push-pull molecule 40 containing long alkyl chains issynthesized. The molecule 40 is obtained by a palladium catalyzedcoupling reaction 42 between 4-bromo-benzonitrile 44 and thecorresponding secondary amine 46.

Ten percent of the push-pull molecule 40 is dissolved in a cholestericmixture. The resulting liquid crystalline mixture is cholesteric at roomtemperature. Suitable liquid crystalline materials are available fromsuppliers such as Merck & Co., Inc. The resulting cholesteric mixture issandwiched between two indium-tin-oxide (ITO) coated glass slides. ITOcoatings provide an electrically conductive surface that at the sametime offers a high optical transparency. The bottom of the display iscoated with a black absorptive layer. The thickness of the cholestericlayer is fixed, for example, by using glass spacers.

A range of dipolar dopants can be used. This range can be varied fromvery low concentrations (for example 1% by weight) to highconcentrations. However, the high concentration is limited by themiscibility or compatibility of the dopant in the liquid crystallinemixture.

With reference again to FIG. 2, when a 25 V electric field 26 is appliedin a vertical direction a shown in the figure, perpendicular to thesubstrates, the display assumes a black appearance to an observer due tothe black absorptive layer 16 and the transparency of the cholestericmixture 24 in the focal-conic black state 28.

If the electric field is removed, the black color is maintained.However, when the same voltage is applied in the opposite direction fora short period of time, less than 1 second for example, the sample takeson a colored state 32 due to the aforementioned optical property ofselective reflection by cholesteric molecules in a planar state, givingrise to a selective color being observed such as white-green forexample. This state is also stable after the electrical field is turnedoff. If the electric field 26 is re-applied in any direction, thedisplay again becomes black as viewed by the observer. By comparison, adisplay made of the same cholesteric liquid crystal mixture, but withoutthe dipolar dopant added, requires a voltage higher than 100 V to obtainthe colored state.

Planar alignment layers may be optionally be coated on the surface ofthe electrodes. This results in improved planar alignment of the helicesin the color reflecting state which provides more saturated reflectedcolor. Surface alignment layers for planar alignment are known and theyinclude for example thermally cross-linkable polyimides as for examplethose produced by Nissan Chemical Ind., Ltd. Improved planar alignmentis provided by rubbing the polyimide coated substrates.

It is to be appreciated that selective areas of a display andsurrounding areas can be switched independently so that an image can begenerated on the display, and stored when the voltage providing theexternal electric field is turned off, thereby removing the electricfield or fields. Each of selective display areas can be switched asnecessary, to either a black or colored state.

While particular embodiments have been described, alternatives,modifications, variations, improvements, and substantial equivalentsthat are or may be presently unforeseen may arise to applicants orothers skilled in the art. Accordingly, the appended claims as filed andas they may be amended are intended to embrace all such alternatives,modifications variations, improvements, and substantial equivalents.

1. A cholesteric display reflecting in the visible range of from about400 nm to about 730 nm comprising: (a) a liquid crystalline mixture; and(b) a dipolar dopant dissolved in the liquid crystalline mixture.
 2. Thecomposition of claim 1, wherein the dipolar dopant comprises a push-pullmolecule containing long alkyl chains.
 3. The composition of claim 1,wherein the dipolar dopant is present in an amount from about 1% byweight to the limit of compatibility of the dipolar dopant and theliquid crystalline mixture.
 4. The composition of claim 1, wherein thedipolar dopant is present in an amount from about 1% by weight to about25% by weight with respect to the amount of the liquid crystallinemixture.
 5. The composition of claim 1, wherein the dipolar dopant ispresent in an amount from about 1% by weight to about 15% by weight withrespect to the amount of the liquid crystalline mixture.
 6. Thecomposition of claim 1, wherein the dipolar dopant is present in anamount from about 1% by weight to about 10% by weight with respect tothe amount of the liquid crystalline mixture.
 7. A process for producinga cholesteric display device comprising: (a) providing a cholestericcomposition reflecting light in the visible range including a dipolarmolecule and a liquid crystalline mixture; and (b) inserting thecomposition into a liquid crystal display cell.
 8. The cholestericdisplay device produced by the process of claim
 7. 9. The process ofclaim 7, wherein the dipolar dopant is added to the liquid crystallinemixture in an amount from about 1% by weight to about 25% by weight withrespect to the amount of the liquid crystalline mixture.
 10. The processof claim 7, wherein the dipolar dopant is added to the liquidcrystalline mixture in an amount from about 1% by weight to about 15% byweight with respect to the amount of the liquid crystalline mixture. 11.The process of claim 7, wherein the dipolar dopant is added to theliquid crystalline mixture in an amount from about 1% by weight to about10% by weight with respect to the amount of the liquid crystallinemixture.
 12. A device comprising a liquid crystal composition includinga cholesteric liquid and a dipolar dopant, wherein the liquid crystalcomposition reflexes light in the visible range of the spectrum when inthe planar state, is switchable between a focal-conic state and a planarstate in the presence of an electric field, and is stable in therespective states when the electric field is removed.
 13. The device ofclaim 12, wherein the dipolar dopant comprises a push-pull moleculecontaining long alkyl chains.
 14. The device of claim 12, wherein theliquid crystal composition is switchable between the focal-conic stateand the planar state in the presence of an electric field generated byan applied electric field of approximately 4 volts/micron or less. 15.The device of claim 12, wherein the dipolar dopant is present in anamount of from about 1% by weight to the limit of compatibility of thedipolar dopant in the cholesteric liquid.
 16. The device of claim 12,wherein the dipolar dopant is present in an amount of from about 1% byweight to about 25% by weight of the dipolar dopant in the cholestericliquid.
 17. The device of claim 12, wherein the dipolar dopant ispresent in an amount of from about 1% by weight to about 15% by weightof the dipolar dopant in the cholesteric liquid.
 18. The device of claim12, wherein the dipolar dopant is present in an amount of from about 1%by weight to about 10% by weight of the dipolar dopant in thecholesteric liquid.
 19. The device of claim 12, further comprising: anelectric field generator that electrically induces the switching betweenthe focal-conic state and the planar state.
 20. The device of claim 12,further including a colored surface positioned to absorb a portion of apredetermined light that passes through the cholesteric liquid in thefocal-conic state such that an observer sees a predetermined color. 21.The device of claim 12, wherein the cholesteric liquid is substantiallytransparent to the predetermined light when in the focal-conic state toallow passage of the predetermined light through the cholesteric liquid,and to allow exit of the non-absorbed portion of the predetermined lightfrom the cholesteric liquid.
 22. The device of claim 12, wherein thedipolar dopant is:


23. A cholesteric display device comprising a liquid crystalline mixtureand a dipolar dopant dissolved therein, wherein the resulting mixturereflects light in the visible range of the spectrum when in a planarstate.